2001 Fiscal Year Final Research Report Summary
Study on generation of conjugated heterocumulene
| Project/Area Number |
12470484
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | University of Shizuoka |
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Principal Investigator |
SATO Masayuki Professor, School of Pharmaceutical Sciences, University of Shizuoka, 薬学部, 教授 (80004654)
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| Co-Investigator(Kenkyū-buntansha) |
YUMIKO Suzuki Research Assistant, School of Pharmaceutical Sciences, University of Shizuoka, 薬学部, 助手 (20295546)
IWAMOTO Ken-ichi Instructor, School of Pharmaceutical Sciences, University of Shizuoka, 薬学部, 講師 (50254256)
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| Project Period (FY) |
2000 – 2001
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| Keywords | heterocumulene / acyl ketene / cycloaddition / 1,3-dioxin-4-one / pyridinophane / crown ether / macrocycle |
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| Research Abstract |
1) A series of prochiral 2, 2-bis(hydroxylmethyl)-1, 3-dioxin-4-ones was synthesized by [4+2]cycloaddition of acylketene to protected 1, 3-dihydroxy-2-propanones followed by deprotection of the hydroxyl groups. Dissymmetrization of the prochiral dioxinones by lipase-catalyzed monoacetylation afforded optically active 2-(hydroxymethyl)dioxinones. Intramolecular photo[2+2]cycloaddition of the alkenoates of these alcohols provided an efficient method for regio-, diastereo-, and enantioselective synthesis of cyclobutanols.
2) 4-Hydroxy-2-pyrone derivative bridged by polymethylenes at the 3- and 6-positions are readily synthesized by intramolecular [4+2]cycloaddition of bis(acylketene). On heating with ammonia, the bridge 2-pyrones afforded the corresponding 2, 6-bridged 4-pyridones. This methods have a wide applicability to the bridge length; compounds with a short bridge (n = 8) as well as long bridge (n = 18) are synthesized in satisfactory yields.
3) Dehydroacetic acid derivative bridged by di(ethylene glycol) unit was synthesized by intramolecular [4+2]cycloaddition of a bis(acylketene). Heating the bridged dehydroacetic derivative with ammonia afforded crown ether type pyridinophane (12-crown-4).
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